Crystal structure and Mössbauer studies of the isotypic Fe6-cluster compounds RE15[Fe8C25], RE=Dy, Ho

• New carboferrates RE15[Fe8C25] with RE=Dy, Ho have been synthesized.
• The crystal structures were refined using single crystal X-ray data.
• An orientational relationship between Fe6-clusters and Fe in γ-Fe is outlined.
• 57Fe Mössbauer spectra are in agreement with structural data from X-rays.
• Magnetic hyperfine fields below 50 K are explained by dipolar fields from Dy atoms.

The carboferrates RE15[Fe8C25] (RE=Dy, Ho) were prepared from mixtures of the elements by arc-melting followed with subsequent annealing at 1373 K. The crystal structures were determined from single crystal X-ray diffraction data and revealed an isotypic relationship to Er15[Fe8C25] (hP48, P321). The main feature of the crystal structure is given by Fe6 cluster units characterized by covalent Fe–Fe bonding interactions. 57Fe Mössbauer spectra of Dy15[Fe8C25] were fitted by three subspectra with relative spectral weights of about 3:3:2 which is in general agreement with the crystal structure. Below 50 K, an onset of magnetic hyperfine fields at the three iron sites is observed which is supposed to be caused by dipolar fields arising from neighboring, slowly relaxing Dy magnetic moments.

Fe6-cluster in the crystal structure of RE15[Fe8C25], RE=Dy, Ho. Figure optionsDownload as PowerPoint slide